CN106947323A

CN106947323A - The substrate of fluid composition and its application, labeling method and mark

Info

Publication number: CN106947323A
Application number: CN201710011433.0A
Authority: CN
Inventors: 皮埃尔·德圣·罗曼
Original assignee: Dover Europe SARL
Current assignee: Dover Europe SARL
Priority date: 2016-01-06
Filing date: 2017-01-06
Publication date: 2017-07-14
Anticipated expiration: 2037-01-06
Also published as: CN106947323B; FR3046418B1; EP3190160A1; US10597546B2; FR3046418A1; EP3190160B1; US20170190926A1

Abstract

The present invention discloses a kind of fluid composition at room temperature for liquid, the application of the fluid composition, the method for being handled and/or being marked the substrate using the fluid composition, and substrate.The fluid composition is used in particular for being deflected the fluid composition of continuous jet printing technology print with bifurcation, wherein, the fluid composition is formed not by the electrically charged drop of electric field in printing, and each drop has zero charge, dipole is formed under electric field action, is then deflected by the electric field.Wherein, the fluid composition includes the solvent containing one or more organic solvent compounds and optional water, and the solvent totally has the dielectric constant less than 15；Adhesive；One or more dyestuffs and/or pigment；Also, electrical conductivity of the fluid composition at 20 DEG C is less than or equal to 200 μ S/cm.Substrate, is provided with drying and/or absorbs the fluid composition and the mark obtained or processing.

Description

The substrate of fluid composition and its application, labeling method and mark

Technical field

It is used to print the present invention relates to one kind and/or handles and/or mark and/or encode any kind of substrate (especially Textile substrate), the fluid composition (such as ink composite) of carrier and object, the property of the fluid composition especially fits In by bifurcation deflect continuous hydrojet printing technology utilize have uncharged drop print and/or handle and/or mark and/ Or encode any kind of various substrates, carrier and object.

According to the fluid composition of the present invention, preferably such as ink composite, volatile solvent composition.

More specifically, bifurcation deflection continuous ink jet printing technology is a kind of following technology：In the art, liquid Composition is formed in printing process not by the electrically charged drop of electric field, and each drop has zero charge, and each drop is in electricity Dipole is formed under field action, then above-mentioned drop is deflected by the electric field.

For convenience, the printing technology is designated hereinafter as " SPI " technology.

The invention further relates to the fluid composition (such as ink composite) according to the present invention skill is being printed using hydrojet Application in art especially ink-jet printing technology, i.e., the printing machine or print head of so-called " SPI " technology.

The invention further relates to one kind by hydrojet printing technology, i.e., so-called " SPI " technology is by the liquid combination Thing (such as ink composite) be ejected on substrate, carrier or object (such as textile substrate) print and/or handle and/or Mark and/or print the substrate, the method for carrier or object (object being especially made up of textile).

Present invention finally relates to a kind of substrate, carrier or object (being especially made up of textile), be provided with ( In substrate, carrier or object) dry and/or absorb what is obtained according to the fluid composition (such as ink composite) of the present invention Printing and/or processing and/or mark and/or coding.

Generally speaking, technical field of the invention is hydrojet print field, especially ink-jet printing field.

Background technology

Ink jet printing is a kind of widely-known technique, the technology can print using high-speed as any kind of object, Mark or the arbitrary various information of decoration, bar code, date of sale etc., and these objects with printing equipment without connecing Touch, or even can also on on-plane surface carrier.

Ink-jet printing technology is divided into two major classes：I.e. so-called " drop on demand " (DOD) technology and so-called " continuous inkjet " (CIJ) technology.

" drop on demand " jet is ejected through ink-jet, so-called " bubble " ink-jet, and so-called " piezoelectricity " ink-jet is so-called " valve " ink-jet or last so-called " hot melt " ink-jet are completed by phase change ink jet.

In the case of bubble inkjet, ink evaporates near nozzle, and the evaporation to be located at the resistance for evaporating ink A small amount of ink between device and nozzle sprays.In the case of piezoelectric ink jet, by by piezo-electric crystal or being electrically excited for ceramics The suddenly change of pressure produced by actuator that is being set to movement and being located near nozzle sprays ink droplet.

In the case of " hot melt " ink-jet, ink is without any solvent and makes temperature of the ink on its fusing point.

Therefore " drop on demand " printing can be carried out at room temperature, and piezoelectric ink jet, valve ink-jet or bubble inkjet are exactly this Situation, or carry out at high temperature, such as carried out at about 60 DEG C~130 DEG C, so-called " hot melt " (HM) ink-jet or passes through phase transformation It is particularly the case.Injection is carried out with deflection solid jet to comprise the steps of：The ink feeding of pressurization is contained into piezo crystals In the chamber of body, ink is escaped in containing the chamber of piezo-electric crystal from this as jet by aperture (nozzle).Shaken with the frequency of determination Dynamic piezo-electric crystal causes pressure disturbance in ink jet, and the ink jet vibrates and is gradually dispersed as spherical droplets.Such as Fruit ink is conductive, is placed on the electrode in fluidic paths (jet is broken up in the fluidic paths), so-called " charging electricity Pole " can assign these drops with electrostatic charge.The drop with electric charge deflects and realizes printing in the electric field therefrom.It is not charged The drop (therefore not deflecting) of lotus is recycled in the groove of suction ink, is then recycled in ink loop.

For all types of ink-jet technologies, the viscosity of ink is very low under injection temperation, usually 1cPs to 10cPs Or 15cPs, therefore these technologies are described as low viscosity ink deposition technique.

The injection for carrying out ink by jet, which can ensure that, carry out noncontact to the object for needing not be plane with the high speed of service Formula marks and can arbitrarily change information.

Ink composite suitable for being sprayed and (being sprayed especially by deflection solid jet) by jet should Meet the intrinsic some standards of this technology, the dissolubility, each composition especially with respect to viscosity, in the solvent for cleaning Compatibility, suitable wetability of carrier to be marked etc., and the electrical conductivity in deflection solid jet situation.

, can be to spray orientation with very big stability and simultaneously can be easily in addition, these ink answer rapid draing The mode of cleaning print head is by nozzle without stopped nozzles.

Very various application field of these ink composites needs different ink formulations, suitable for extensive to be marked Substrate (metal, plastics, glass etc.) and meet industrial constraints widely.Particularly, the water resistance of mark may It is important requirement.

The composition that constituting the present invention is used to deflect the ink of the ink-jet of solid jet type is organic products or inorganic product；This A little compositions are colorant materials (such as dyestuff or pigment) in the solvents that one or more are more or less volatilized, resin or viscous Mixture, or optional one or more conductive salts and various additives in water.

Colorant materials according to its in solvent for use it is solvable or insoluble and be referred to as " dyestuff or pigment ".

Therefore substantially insoluble pigment disperseed, and can be opaque or transparent.They are provided for ink Color, opacity or specific optical property, such as fluorescence are (referring to patent or patent application US-A-4 153 593, US-A- 4 756 758、US-A-4 880 465、EP-A-0 289 141、US-A-5 395 432、GB-A-2 298 713).Some In the case of, dyestuff itself also provides enough electric conductivity for ink so that need not add conductive salt.With C.I. solvent blacks 27th, 29,35 and 45 and known dyestuff is such case.

White or the substrate of light color, carrier are marked with black or colored ink, and the dyestuff or face of these ink Expect the dyestuff or pigment of the organic or inorganic based on normally transparent.

Black or dark substrate, carrier are marked with the ink containing opaque pigment, most common opaque pigment It is titanium oxide.

Adhesive or resin are usually predominantly one (or more) kinds of solid polymer compounds, and their selection is by it Dissolubility in selected solvent and they with dyestuff and other additives compatibility and it is most important they It is supplied to the property of ink film to determine (referring to patent or patent application US-A-4 834 799, GB-A-2 286 when drying 402、US-A-5 594 044、US-A-5 316 575、WO-A-96/23844、WO-A-95/29 287)。

Their major function is to make ink adhesion on the maximum amount of carrier or in specific (such as non-porous) load On body.They can also assign proper viscosity to form drop by injection for ink, and they are to ink or more precisely Say most of performance that its resistance to physical erosion and/or resistance to chemical attack are provided to the mark obtained in ground.

The solvent of these ink is most commonly made up of a kind of mixture, and on the one hand the mixture is not including multi-quantity Very sticky volatile solvent compound is so as to quickly dry mark and viscosity regulation is arrived into required value (example Such as 2mPa.s~10mPa.s), and on the other hand include lesser amount of more viscous volatility it is smaller and dry slower solvent with The ink during the stop phase of printing equipment is avoided to be dried in nozzle (referring to patent or patent application US-A-4 155 767th, WO-A-92 14794, WO-A-92 14 795 and US-A-4 260 be 531).

As shown in patent US-A-4 567 213 and US-A-5 637 139, most-often used volatile solvent compound It is the alcohol, ketone or ester of low molecule amount.These solvated compoundses that can be referred primarily to have：Methanol, ethanol, 1- propyl alcohol and 2- third Alcohol, acetone, methyl ethyl ketone (MEK) and methyl iso-butyl ketone (MIBK).

With it is obvious dry delay feature less volatile solvated compoundses be typically it is single or with it is following other The ketone (such as cyclohexanone) quoted in document US-A-4 024 096 and US-A-4 567 213 of solvent combination, ethylene glycol Ether, the ether mentioned in document US-A-4 155 767 and acetal (such as furans Huo dioxanes), dimethylformamide or diformazan Base sulfoxide (US-A-4 155 895), lactone (EP-A-0 034 881), 1-METHYLPYRROLIDONE (EP-A-0 735 120), two Alcohol (WO-A-96 23 844) and even aliphatic hydrocarbon (US-A-4 166 044) or water, may be referred to document US-A-4 in this respect 153 593, GB-A-2 277 094 and FR-A-2 460 982.

In general, it must be expired by deflecting the main or most of solvated compoundses for the ink that solid jet is sprayed The a number of standard of foot, particularly：

Their volatility must be enough to make ink rapid draing on carrier to be marked, but should not be too high so as to special Being will not the too fast evaporation in printing machine during stop phase；

Their adhesives relative to ink, dyestuff or pigment dispersion and the solvent energy relative to carrier to be printed Power (solvability) allows for assigning dry ink with good adhesiveness；

Their influences to health, i.e. its toxicity, harmfulness, excitant and inflammability must be reduced；

They allow for keeping optional ink to be taken in sterile；

Finally, they must have what is kept ionic species (salt that its electric conductivity is such as assigned to ink) dissolving and dissociate Ability.

The additive includes：The dispersant of pigment can be disperseed；Change the wettability of ink or the table of penetration capacity Face activating agent (USA5395431), is particularly varied or adjusted the surfactant of either statically or dynamically surface tension, such as purchased fromCompanyFC 430；The inhibitor of the corrosion of the Salt treatment of foregoing electrical conductivity is provided (referring to document EP-A- 0510752nd, US-A-5102458), or the corrosion of protection ink antibacterium and the additive of other microbial reproductions, aqueous oil Particularly useful microorganism is biocide, bactericide, fungicide etc. in ink；PH adjusts buffer (referring to EP-A- 0735120)；Defoamer.

Optional conductive salt is the electrical conductivity needed for ink provides electrostatic deflection.Document US- is may be referred in this respect A-4 465 800。

The dissolvable in the solvent medium of ink of all kinds is used in the salt for providing electric conductivity and can be dissociated can Ionised species.

For solvent most solvated compoundses be water ink, assign ink problem is not resulted in generally with electric conductivity, Because most of water-soluble products are ionizable materials.

But aqueous medium can not realize multiple formulations because the solvent power of water is limited, and water evaporation rate too Slowly, so as to benefit from the high printing speed of ink-jet permission.

Various organic solvent compounds are conversely, there exist, it has by force molten relative to many polymer and dyestuff Xie Li, this allows to prepare the larger numbers of quick-drying oil with excellent adhesion in various types of substrates Ink.

On the other hand, in these organic medias, only when solvated compoundses are fully dissociated, i.e. the dielectric at them is normal Electric conductivity is obtained when number and they sufficiently high dipole moment.

More precisely, electric conductivity is provided to ink by salt (being typically conductive salt).But, if solvent relative to Material present in ink dissociates and produces ion, then these salt are only ink and provide electric conductivity.

It has been generally acknowledged that the solvated compoundses that dielectric constant is less than about 15 can not give ink institute by the continuous inkjet of deflection The electrical conductivity needed.

In other words, solvent must have the high-k more than 15, to make ion fully dissociate and to be ink Enough electric conductivity is provided.

Generally, it is considered that for such injection with jet, the minimum conductivity that ink must have is about 500 μS/cm。

In addition, above-mentioned salt may be unfavorable for the stability of ink.

Therefore, in order to be sprayed by deflecting solid jet technology, ink can be only with only molten comprising dissociative Immunomodulator compounds or the main solvent for including such dissociative solvated compoundses are prepared.

In other words, the solvent of the low-k of non-dissociative cannot be used for the ink of standard " CIJ " technology of classics In composition.

Therefore, document EP-A0-1 858 990 (WO-A1-2006/097502) is taught for deflecting continuous jet printing The solvent of the ink of technology must have greater than about 15 dielectric constant, with abundant dissociating ions material (such as salt) and assign oil Ink is with enough electric conductivity.

Document EP-A0-1 200 530 (WO-A1-01/09255) is taught：Dielectric constant is 7.1 1,3- dioxolanes With not enough dissociation capability, and solvent that must be stronger with another dissociative is combined, is printed with assigning deflection continuous inkjet The ink of brush technology is with necessary electric conductivity.

Patent US-B2-8,282,724 is taught：Dielectric constant has not enough dissociation energy for 2.5 ethylal Power, and solvent that must be stronger with another dissociative combined, to assign the ink of deflection continuous ink jet printing technology with must The electrical conductivity wanted.

But, it is always necessary to the volatility of these solvated compoundses is enough to make ink fast rapid-curing cutback on carrier to be marked It is dry,

However, there are considerably less solvated compoundses is both volatile and dissociative.

These be both volatile and dissociative solvated compoundses almost be only low molecule amount ketone and alcohol, it is all Such as, acetone, methyl ethyl ketone, methanol and ethanol, and using some (such as methanol) in these solvated compoundses due to it Toxicity but it is undesirable.

The volatility ester suitable with alcohol with the ketone of low molecule amount has the dielectric constant less than 10, and can not be used as oil The sole component of the solvent of ink.

Finally, the ink for the mark based on volatile solvent compound, coding or printing must contain available deflection The ionizable solvated compoundses of major part of continuous jet printing technology injection, which greatly limits these solvated compoundses It may select, therefore also limit the possibility selection of adhesive and dyestuff, and finally significantly limit the possibility formula of ink.

In addition, having developed hydrojet especially ink-jet printing technology recently, for the sake of convenience, we then will be referred to as " SPI " technology with avoid repeat, wherein, " SPI " is the abbreviation of " super piezo ink-jet (super piezo ink jet) ".

" SPI " technology of being somebody's turn to do both is different from so-called " drop on demand " (DOD) technology, also different from so-called " continuous inkjet " (CIJ) technology.

Briefly, should " SPI " technology can be defined as bifurcation " CIJ " and deflect continuous jet printing technology, and for printing The continuous jet printing technology of deflection of the drop ejected of brush each with non-zero net charge is different, and drop does not have in the art Have electrically charged by electric field, each drop has zero charge, and each drop forms dipole under electric field action, then above-mentioned liquid Drop is deflected by the electric field.

" bifurcation " refers to：

In the presence of the first track of the drop for printing, and second for the drop that makes ink recirculation

Track.In the second track of drop, drop is recycled in the groove of suction ink, is then followed again

Ring is into ink loop.

The information of N number of pixels tall needs the print head with N number of nozzle.

It should be noted that in " CIJ " deflects continuous jet printing technology, the drop of deflection is the drop of printing, and In so-called " SPI " technology, undeflected drop is the drop for printing.

In following documents [1] and [2] that " SPI " technology is so widely described clearly to refer to herein, and they Full text be all incorporated into this specification：

Document WO-A2-2005/070676 (corresponding to document FR-A1-2851495 and US-B2-7192121) [1] description In the art how by means of being provided with the print head formation drop of interior activating system.

More specifically, according to the claim 1 of the document, the document is related to a kind of ink-jet printer, including：

Print head with one or more nozzle, the print head has the encapsulation header main body for each nozzle,

The hydraulic path of ink, including launch one of the print nozzles of ink jet pressurizeed hydraulic pressure company with the axle along nozzle Logical excitation cavity,

Interior arrangement for exciting the ink jet launched by nozzle, the interior arrangement is with being encapsulated in the excitation cavity Ink is mechanically connected, and these devices are acted on the jet launched by nozzle controllably to break up the jet, and

The device for the ink that substrate is received is not printed for reclaiming,

Electric control signal maker, receives control signal and sends excitation signal to excitation apparatus,

The charging electrode structure in upstream and downstream region is limited around the axle of the nozzle, the downstream area is than the upstream Domain farther away from the nozzle, the upstream electrode and downstream electrode of the structure be connected with potential source so as to keep in a region with Kept in the equal current potential of the current potential of ink in the main body of the print head, and another region in that region with The different current potential of the current potential of ink in the main body of the print head,

The deflection electrode structures set in the downstream axial of the charging electrode structure,

Characterized in that, electric control signal maker is to excitation apparatus sending signal, the signal causes on this The upstream in trip region breaks up position and intermittently controllably breaks up jet, so as to intermittently form drop, therefore the jet is divided into Drop and fragment, and also result in and position is broken up in downstream continuously controllably break up the jet or the fragment of the jet, by Therefore the solid jet of nozzle transmitting is converted into the electrically charged and neutral of continuous series after the downstream area Ink droplet.

According to the claim 13 of the document, the document further relates to a kind of method by the press printing carrier, Wherein, make, by the ink jet classification of the nozzle transmitting of the printing machine, the first liquid formed in substrate a little to be incided to be formed Drop and fragment, part,

Characterized in that,

Jet is classified as the first drop as the fragment produced by being classified the jet, and fragment is further classified as second Drop, the second drop produced by being classified by the last time is directed to groove.

According to the claim 14 of the document, the document finally refers to a kind of ink jet printer head, including：

Print head with one or more nozzle, the print head has the print head being especially encapsulated in each nozzle Main body (1),

The hydraulic path of ink, including with launching one of the print nozzles of ink jet pressurizeed hydraulic pressure along the axle of the nozzle The excitation cavity of connection,

The interior arrangement for the ink jet launched by nozzle is excited, the interior arrangement and the ink being encapsulated in the excitation cavity Mechanically connect, these devices are acted on the jet launched by nozzle controllably to break up the jet, and

Characterized in that, electric control signal maker is to excitation apparatus sending signal, the signal causes on this The upstream in trip region breaks up position and intermittently controllably breaks up jet, and also results in position is broken up in downstream continuously controllably The jet or the fragment of the jet are broken up, therefore the solid jet launched by the nozzle is converted after the downstream area For the electrically charged of continuous series and uncharged drop.

Document FR-A1-2906755 (corresponding to document WO-A1-2008/040777 and US-B2-8162450) [2] description In the art how drop is set to classify under variable field action.

More specifically, according to the claim 1 of the document, the document is related to a kind of side for being used to deflect liquid jet Method, including：

Along the jet of hydraulic trajectory (A) the formation conducting liquid that (v) is flowed out by the nozzle of pressurizing chamber at a predetermined velocity,

By the way that potential is applied to a series of multiple deflecting electrodes along the hydraulic trajectory (A) direction, to produce along institute State hydraulic trajectory (A) variable electric field (E), the electrode is isolated from each other and forms network, length of the network in whole network (L) extend on along the electrode plane parallel to the hydraulic trajectory (A), wherein, each electrode of the application into the network Potential is variable, and the potential of all electrodes applied into the network has zero-time and spatial averaging,

Using the electric field (E), moved by the electric charge in the jet, make the jet deflection.Following documents [3], [4] and [5] describe the improvement to the technology in document [1] and [2], these documents are clearly referred to herein, and they Full text be all incorporated into this specification.

Document FR-A1-2952851 (corresponding to document WO-A1-2011/061331 and US-B2-8540350) [3] description How interaction adjacent nozzle between is avoided by compensating mechanical cross talk.

More specifically, the document is related to the continuous ink jet printing machine including print head, it is characterised in that it includes being used to mend The device of mechanical cross talk between adjacent chambers is repaid, while excitation pulse is transmitted to excitation cavity, these devices are transmitted for compensating The pulse of mechanical cross talk on each line for serve the chamber actuator adjacent with excitation cavity.

Specifically, the claim 1 of the document is related to a kind of continuous ink jet printing machine including print head, including：

Multiple excitation cavities, align along the alignment axis of these excitation cavities,

Flat diaphragm, the part of the flat diaphragm constitutes the wall of each excitation cavity,

Multiple nozzles, each nozzle respectively with a hydraulic communication in the excitation cavity,

At least one charging electrode and a deflecting electrode positioned at the nozzle downstream,

Multiple electromechanical actuators, are each respectively mechanically attached to the diaphragm portion for the wall for constituting each excitation cavity,

A plurality of excitation line, every line is used to excitation pulse being respectively transmitted to different actuators,

The device of data to be printed for handling, described device receives the carrier signal for being loaded with data to be printed, and And excitation pulse is provided according to these data, the excitation line is sent to,

Characterized in that, it further comprises the device for compensating mechanical cross talk between adjacent chambers, passed to excitation cavity While sending the excitation pulse in excitation line, these devices are transmitted is serving the actuator adjacent with excitation cavity for compensating The pulse of mechanical cross talk on each line of chamber.

According to the claim 2 of the document, the document is related to a kind of print head of continuous ink jet printing machine, including：

According to the claim 7 of the document, the document finally refers to a kind of printing for being used to mitigate continuous ink jet printing machine The method of the consequence of mechanical cross talk between the adjacent excitation cavity of head, the print head of the continuous ink jet printing machine includes flat diaphragm, The part of the flat diaphragm constitutes each wall in these excitation cavities；Positioned at least one charging electrode in nozzle downstream and one Individual deflecting electrode；With the electromechanical actuator for exciting each chamber；With a plurality of excitation line, every line is used to transmit excitation pulse Give each actuator, it is characterised in that while excitation pulse is sent to the actuator of excitation cavity, compensated pulse is sent To each chamber adjacent with excitation cavity, each actuator cavities adjacent with excitation cavity are sent to.

Document FR-A1-2971199 (corresponding to document WO-A1-2012/107461 and US-A1-2013/307891) [4], A kind of printing control method is described, wherein carrying out reversing between two adjacent nozzles.

More specifically, according to the claim 1 of the document, this document describe a kind of for controlling to be provided with print head The printing of bifurcation continuous ink jet printing machine or the printing of the print head of such printing machine are with the print moved relative to print head The method of printed patterns on brush carrier, the print head includes：

So-called multi-nozzle liquid droplet generator, including：

Main body, including：

Excitation cavity, each excitation cavity can receive the ink of pressurization,

Injection nozzle, each injection nozzle is connected with excitation cavity, and each injection nozzle can spray along its longitudinal axis Ink jet is penetrated, the nozzle aligns and arranged at grade along alignment axis,

Actuator, each actuator is mechanically connected with excitation cavity, and can be made in response to pulse command by connecting with the chamber The jet of logical nozzle injection is broken up at the nozzle plane Lbr,

Yoke assembly below nozzle, it includes from upstream side to downstream：

Bucking electrode,

First dielectric layer adjacent with the bucking electrode,

At least one pair of deflecting electrode, each deflecting electrode is all surrounded in both sides by dielectric layer,

According to this method：

The information of relative position of the carrier relative to the head is determined,

Alternating voltage anti-phase relative to each other is provided for same a pair of electrodes,

Pulse is sent to actuator to spray by the nozzle connected with mechanically connecting the chamber of the actuator Jet breaks up and formed the drop that can not be deflected electrode charge at the plane Lbr apart from the nozzle or by deflecting electrode The jet segments of electrostatic influence,

Pulse is controlled to minimize the total electrical charge on the jet segments being included in the electrostatic influence volume of deflecting electrode.

According to the claim 9 of the document, it is continuous that the document further relates to a kind of bifurcation for being used to implement the control method Ink-jet printer.

Document FR-A1-2975632 (corresponding to document WO-A1-2012/163830 and US-A1-2014/168322) [5] Describe how that print speed printing speed is increased into 10m/s from 2m/s by means of droplet generator.

More specifically, according to the claim 1 of the document, this document describe a kind of for bifurcation continuous inkjet multiinjector The print head of printing machine or such printing machine is with the printing side of the printed patterns on the printing carrier moved relative to print head Method, the print head includes：

Multi-nozzle liquid droplet generator, including：

Main body, including：

One or more pressurizing chambers, each pressurizing chamber can receive the ink of pressurization,

With the injection nozzle of pressurizing chamber hydraulic communication, and each injection nozzle can line (A) injection tool along its longitudinal axis There is speed V_jInk jet, the nozzle aligns and arranges at grade along alignment axis,

Actuator, can be such that the jet sprayed by nozzle breaks up to form a series of drops in response to pulse command,

According to this method, carrier has on speed Vs, carrier moving direction between continuous pixel relative to the head Distance is Dii, and according to this method, first kind drop and Equations of The Second Kind drop, first kind drop are formed by breaing up jet In each drop there is the first volume, all first volumes are substantially identical to one another, and Equations of The Second Kind drop has each other need not be identical The second volume, but all Equations of The Second Kind drops all have the volume differed with the volume of first kind drop,

An at least class liquid is applied to by the deflecting force for being possible to break up the track of first kind drop and Equations of The Second Kind drop Make the track differentiation that first kind drop and Equations of The Second Kind drop are followed in drop, track and the printing carrier of first kind drop meet, And the track of Equations of The Second Kind drop is met with reclaiming the groove of these drops,

Produce one with contiguous pixels to be printed in the extension of position that they can be printed at the time of related information,

For the process black pixel after white pixel, first kind drop and Equations of The Second Kind drop, these first kind liquid are formed Drop and the accumulative of Equations of The Second Kind drop form extension period of the period equal to or more than pixel.

Document [1], [2], [3], [4] and [5] is applied to printing machine, print head and method in these documents without description Specific ink, do not instruct yet select these ink standard enlightenment.

Accordingly, it would be desirable to ink composite, more generally, it is necessary to be specially adapted for so-called " SPI " technology as defined above And process, method, print head and the printing machine that can be used in particular for described in document [1], [2], [3], [4] and [5] and at this The fluid composition formerly clearly discussed in specification.

The purpose of the present invention especially satisfaction carries out this of the composition of the mark, coding or printing of all carriers with ink-jet Planting needs, and offer is particularly suitable for use in so-called " SPI " technology and can be used in particular for formerly clearly begging in this manual The fluid composition of process, method, print head and printing machine described in the document [1], [2], [3], [4] and [5] of opinion.

Another object of the present invention is to provide mark for all carriers by deflecting continuous jet printing technology, compile Code or printing fluid composition, particularly volatile ink composite, wherein the solvated compoundses of this composition can It can select significantly to be widened, to have the very big free degree in the preparation of these fluid compositions.

Especially, the purpose of the present invention be by deflect continuous jet printing technology provide mark for all carriers, Coding or the fluid composition of printing, particularly ethereal oil ink composition, wherein it is possible to not reduce the situation of printing quality The solvent of the non-dissociative of lower use low-k.

The content of the invention

According to the present invention, this purpose and other purposes are with the fluid composition (combination of liquid for being at room temperature liquid Thing), such as ink composite is realized, the fluid composition is used in particular for deflecting continuous jet printing technology print with bifurcation Fluid composition, wherein, the fluid composition is formed not in printing process by the powered drop of electric field, each drop With zero charge, each drop forms dipole under electric field action, and then the drop is deflected by the electric field, and its feature exists In the fluid composition includes：

A) solvent containing one or more organic solvent compounds and optional water, the solvent overall (entirety) has Less than the dielectric constant of (being less than) 15；

B) adhesive；

C) one or more dyestuffs and/or pigment；

And：

D) electrical conductivity of the fluid composition at 20 DEG C is less than or equal to 200 μ S/cm, preferably lower than or equal to 150 μ S/cm, more preferably less than or equal to 100 μ S/cm.

Generally, solvent is less than 15 organic solvent compound comprising at least one dielectric constant, and further optional One or more dielectric constants are more than or equal to 15 organic solvent compound and/or water.

, can be with it should be pointed out that the dielectric constant of the mixture of solvent can be measured ideally, or if not so Estimated by the dielectric constant of each component and be weighted by their mass ratio.

It is noted that electrical conductivity is according to principle well known to the skilled person, such as described by following network address： http://fr.wikipedia.org/wiki/Conductim%C3%A9trie, is measured with commercial instruments.

Electrical conductivity can be measured according to following standard：ASTM D1125-14：" electrical conductivity of water and the mark of resistivity Quasi- method of testing ".

Electrical conductivity can be with for exampleThe commercially available conductometer of company is measured.

Hereafter, when being related to viscosity, it can be measured according to following standard：DIN 53019-1：It is " viscous by rotation Spend viscosity measurement and flow curve ".

Dynamic viscosity can be for example using coaxial cylinder viscometer, such as" Ku Aite " type of company is same Axle cylinder viscosimeter is measured.

Hereafter, when being related to particle diameter, it can be measured according to following standard：ISO 22412:2008.

Particle diameter for example can be passed through using the technology of also referred to as " quasi-elastic light scattering (QELS) " of " photon auto-correlation "The hondrometer of company is measured.

Hereafter, when being related to molecular weight, it can use polystyrene standard by GPC (or spatial exclusion chromatography) Measure.

Term " fluid composition " not only covers ink, and covers the liquid for being referred to as " functional liquid ".Feature Liquid can deposit any liquid of the material with specific function, and specific function is such as, but not limited to：Colouring function, Medical functions, pharmic function, water-proof function, fixing function, fire resisting function, conducting function, insulation function, antiforge function, especially It is the pretreatment and post processing of textile.

Generally it can be thought that, the difference of functional liquid and ink is：Ink is substantially coloured, and feature liquid Body is not necessarily coloured.

The above-mentioned pretreatment of textile may be generally defined as preparing before printing textile or auxiliary it is fixed or The processing of suitable regional protectionism textile.The post processing of above-mentioned textile can be various, and be this area skill Known to art personnel.

" room temperature " generally refers to 5 DEG C~30 DEG C, preferably 10 DEG C~25 DEG C, more preferably 15 DEG C~24 DEG C, more preferably 20 DEG C~ 23 DEG C of temperature.It should be understood that ink is liquid at atmosheric pressure.

Term " bifurcation " is known in the art, and hereinbefore it is clearly defined.

It is particularly adapted for according to the fluid composition of the present invention with a kind of very specific printing technology, i.e. bifurcation deflection company The fluid composition of continuous jet printing technology print, wherein, aforesaid liquid composition is formed in printing process not by electric field Powered drop, each drop has zero charge, and each drop forms dipole under electric field action, and then above-mentioned drop is described Electric field is deflected.

For the sake of convenient, this technology is referred to as " SPI ".

Composition for any SPI technologies according to the fluid composition of the present invention, i.e., for own " SPI " process, The composition of method, and it is applied to all printing machines and print head according to the technical operation.

Therefore, it is emphasized that according to the present invention fluid composition be used for above-mentioned document [1], [2], [3], [4] or the process described in [5], method, printing machine and print head；For in these documents for such as hereinbefore clearly discussing Process, method, printing machine and print head；And for by described in above-mentioned document [1], [2], [3], [4] or [5] at least Two processes, method, the combination of the feature of printing machine or print head are limited, or by hereinbefore clearly discussing at least The combination of any process, method, printing machine or print head that two processes, method, the combination of printing machine or print head are limited Thing.As combination, document [1] and the combination of [2] or document [1] and [2] and one or many in document [3]~[5] are can be mentioned that Individual combination.

It means that be configured specifically for according to the ink composite of the present invention with specific " SPI " technology print, because This according to the fluid composition of the present invention with for " DOD " printing technology or standard " CIJ " printing technology (i.e. " CIJ " technology) Fluid composition essence is different.

More precisely, being to deflect continuous jet printing technology with " CIJ " to enter first according to the fluid composition of the present invention The fluid composition of row printing, according to this it is simple the fact, it is clear that be different from according to the fluid composition of the present invention with demand The fluid composition that drippage (DOD) printing technology is printed.

Secondly, formed according to the fluid composition of the present invention in printing process not by the electrically charged drop of electric field, often Individual drop has zero charge, and each drop forms dipole under electric field action, and the composition for being used for standard " CIJ " technology is formed Electrically charged drop.

Finally, printed drop deflection using electric field according to the fluid composition of the present invention, this point also makes its bright The aobvious fluid composition being different from for DOD technologies.

It is characterised by according to the fluid composition of the present invention：It further simultaneously have all characteristic a), b), c) and d)。

There is all feature a), fluid composition (such as ink composite) b), c) and d) never by existing skill simultaneously Art is described or implied.

It has been found that the fluid composition according to the present invention with this all four features is particularly well applicable for So-called " SPI " printing technology stated.

These features are further by the fluid composition according to the present invention with being used for " DOD " printing technology or standard " CIJ " The fluid composition of printing technology is differentiated, and assigns the fluid composition according to the present invention compared to for " DOD " printing The advantageous property of the fluid composition of technology or " CIJ " printing technology.Therefore, according to feature a), according to the liquid of the present invention Composition (such as ink composite) includes the solvent containing one or more organic solvent compounds and optional water, described molten Agent overall (being used as entirety) has the dielectric constant less than 15.

Generally, above-mentioned solvent is less than 15 organic solvent compound, and further bag comprising at least one dielectric constant It is more than or equal to 15 organic solvent compound and/or water containing optional one or more dielectric constants.

Fluid composition (such as ink composite) for " CIJ " printing technology is generally less than not comprising dielectric constant 15 this solvent.

In addition, according to feature d), being less than or equal to 200 μ according to electrical conductivity of the fluid composition of the present invention at 20 DEG C S/cm, preferably lower than or equal to 150 μ S/cm, more preferably less than or equal to 100 μ S/cm, and it is used for the liquid of " CIJ " printing technology Electrical conductivity of the body composition at 20 DEG C is more than or equal to 500 μ S/cm, preferably greater than 500 μ S/cm.

It is to be used in particular for pair using SPI technologies are referred to as according to the fluid composition (such as ink composite) of the present invention State deflects the fluid composition of continuous jet printing technology print.However, SPI technologies usually require the electrical conductivity of minimum.Therefore, According to the minimum value of electrical conductivity of the fluid composition (such as ink composite) at 20 DEG C of the present invention be usually 1 μ S/cm~ 10μS/cm.In other words, 1 μ S/cm, 2 will be generally greater than or equal to according to electrical conductivity of the fluid composition of the present invention at 20 DEG C μ S/cm, 3 μ S/cm, 4 μ S/cm, 5 μ S/cm, 6 μ S/cm, 7 μ S/cm, 8 μ S/cm, 9 μ S/cm or 10 μ S/cm.

Therefore, (1 can not can be included for the μ S/cm of 1 μ S/cm~200 according to the electrical conductivity of the fluid composition of the present invention μ S/cm and 200 μ S/cm, i.e. scope is：More than 1 μ S/cm and less than 200 μ S/cm；Or 1 μ S/cm or 200 μ can not be included S/cm；Or 1 μ S/cm and 200 μ S/cm can be included), the μ S/cm of particularly 2 μ S/cm~150 (can not include 2 μ S/cm and 150 μ S/cm, i.e. scope is：More than 2 μ S/cm and less than 150 μ S/cm；Or 2 μ S/cm or 150 μ S/cm can not be included；Or Person can include 2 μ S/cm and 150 μ S/cm), the μ S/cm of also particularly 5 μ S/cm~100 (can not include 5 μ S/cm and 100 μ S/ Cm, i.e. scope are：More than 5 μ S/cm and less than 100 μ S/cm；Or 5 μ S/cm or 100 μ S/cm can not be included；Or can be with Including 5 μ S/cm and 100 μ S/cm), the μ S/cm of or even 10 μ S/cm~100 (can not include 10 μ S/cm and 100 μ S/ Cm, i.e. scope are：More than 10 μ S/cm and less than 100 μ S/cm；Or 10 μ S/cm or 100 μ S/cm can not be included；Or can With including 10 μ S/cm and 100 μ S/cm).

Generally there is 2mPa.s~10mPa.s viscosity according to the fluid composition of the present invention.

Proved in surprising mode, when searching is particularly suitable for the fluid composition of so-called " SPI " technology, Just because of according to the present invention fluid composition design by for so-called " SPI " technology, the composition is with being used for The fluid composition of " DOD " printing technology or " CIJ " printing technology, which is compared, can have favourable characteristic.

Also proved in surprising mode, according to the fluid composition of the present invention although can be in terms of its preparation (especially with regard to solvent) has the scope of non-constant width, impressionability is remained in that under low conductivity, low conductivity is Less than or equal to 200 μ S/cm, more preferably less than or equal to preferably lower than or equal to 150 μ S/cm, 100 μ S/cm.

In standard " CIJ " printing technology, the net charge that drop is carried is passed through in the charging identical mode with capacitor Electrostatic influence at the surface of jet is induced.

The electric charge depends on the duration of charging voltage, and additionally depends on the electrical conductivity of ink.The net electricity provided Lotus changes over time, until obtaining final asymptotic value.When electrical conductivity is not enough, the end value can not be obtained in time, and should Electric charge will significantly depend on jet at the time of break up generation.

On the contrary, in so-called " SPI " technology, because the net charge of drop is zero, the precision for breaing up the moment is not crucial 's.

Therefore, according to present invention has demonstrated that, can use Conductivity Ratio be used for standard " CIJ " technology fluid composition Much lower fluid composition (such as ink), and mark or printed matter are assigned simultaneously with superior quality.

As described above, as the electrical conductivity of the fluid composition for standard " CIJ " printing technology, according to the present invention's Electrical conductivity of the fluid composition at 20 DEG C is no larger than or equal to 500 μ S/cm, and is less than or equal to 200 μ S/cm.

Led as described above, being provided by salt for the fluid composition (such as ink composite) of standard " CIJ " printing technology Electrically.But if solvent is dissociation to ion, then these salt are only capable of providing electric conductivity, and these salt are to fluid composition Stability have negative effect.

Solvent for the fluid composition (such as ink composite) of standard " CIJ " printing technology, which must have, is more than 15 High-k, so as to abundant dissociating ions.

According to the present invention, because the electrical conductivity of fluid composition is low, so the solvent chemical combination of the low-k less than 15 Thing is made available by, and they cannot be used for standard CIJ compositions.

Therefore, the possibility selection of these solvated compoundses is significantly widened.Especially, the volatile solvent that can be selected The quantity of compound is dramatically increased, because the volatile solvent compound no longer must be as situation so far, only It is unique to be selected from the solvated compoundses with high-k.

Therefore, these solvated compoundses can (such as they be not present according to the standard in addition to their dielectric constant Harmfulness) selected.

In addition, the amount of the conductive salt in the fluid composition of the present invention is typically smaller than in standard CIJ composition Conductive salt amount (see below), this eliminates the negative effect to the stability of fluid composition due to the salt.Change Sentence is talked about, and is containing less salt and therefore more stable composition according to the composition of the present invention.

Advantageously, polarity can be used than ketone, water, acid amides or the smaller solvated compoundses of alcohol, and therefore can be had The smaller composite formula of composition of the evil sex ratio such as containing ketone or acid amides.

In " CIJ " technology, high density, the liquid of proportion are imprintable, because high-quality drop is due to inertia Effect and be not enough to by electricity source (electric origin) deflecting force deflection.

On the contrary, according to present invention has demonstrated that, in so-called " SPI " technology, printed drop is not deflected Drop, therefore according to the scope of the present invention, high density drop is printable.

Advantageously, the granules of pigments in solid particle, such as dispersion can be included according to the fluid composition of the present invention Or binder polymer particle.

Preferably, the full-size of solid particle is 2 μm~10 μm, preferably 2 μm~5 μm.

The average-size or full-size of particle are for example by quasi-elastic light scattering (as usedCompany Zetasizer) or pass through optical diffraction (as useCompany) use laser grain Degree analyzer is measured.

This is also to make to be different from according to the fluid composition of the present invention to print for " DOD " printing technology or standard " CIJ " One feature of the fluid composition of brush technology, and the fluid composition according to the present invention is assigned compared to for " DOD " print The advantageous property of the fluid composition of brush technology or standard " CIJ " printing technology.

In fact, solid particle, such as those solids for being included in the fluid composition of standard " CIJ " printing technology Particle, with the much smaller minimum dimension less than 2mm.

In standard " CIJ " printing technology, the net charge entrained by drop depends on the period of charging electric field and occurs to beat Perfect synchronization between at the time of dissipating.Bulky grain interference is broken up and makes it random, is thus made load electric charge variable, is thus made inclined The positioning of drop is deteriorated and therefore printing is deteriorated after turning.

On the contrary, in so-called " SPI " technology, because the net charge of drop is zero, breaing up the accuracy at moment and being not related to Key.It has therefore proved that：Can be (all by more much bigger than in the fluid composition of standard " CIJ " technology solid particle according to the present invention Such as pigment) it is used in the fluid composition according to the present invention, and any problem will not be produced in printing process, and can be real Existing high-quality mark or processing.No longer it is limited according to the full-size of the solid particle of the fluid composition of the present invention, and only Limited by jet size.

Moreover, for the settlement issues observed by big particle according to the present invention composition in by adjusting viscosity Also become controllable.

In other words, according to the present invention, big solid particle becomes " to can print ", and they are for standard " CIJ " It is imprintable in composition.

Advantageously, it is at least one in the solvent of fluid composition when being further comprised according to the fluid composition of the present invention During solvable polymer (such as binder polymer), then the polymer, which has, is more than 70000 dalton, preferably 75000 roads The dalton of Er Dun~200000, the weight average molecular weight of the dalton of more preferably 80000 dalton~200000.

It should be noted that when polymer is dissolved in solvent (such as according to the solvent of the fluid composition of the present invention), this Necessarily imply that it is dissolved in considered solvent.

This is also to make to be different from according to the fluid composition of the present invention to print for " DOD " printing technology or standard " CIJ " One feature of the fluid composition of brush technology, and the fluid composition according to the present invention is assigned compared to for " DOD " print The advantageous property of the fluid composition of brush technology or " CIJ " printing technology.

In fact, the polymer contained in the fluid composition for " CIJ " printing technology has no more than 70000 Molecular weight.

It is similar with the mode discussed above for large-sized solid particles, according to the fluid composition of the present invention Can be containing chain very long polymer, and any problem will not be produced in printing process, and high-quality mark can be realized Note and processing.

In other words, according to the present invention, chain very long polymer becomes " to can print ", and they are for standard It is imprintable in the composition of " CIJ ".

Above-mentioned solvent includes one or more solvated compoundses, and the solvated compoundses are selected from organic solvent compound and optional Water.

It should be noted that the gross weight based on ink composite, according to the fluid composition (such as ink composite) of the present invention Generally include minimal amount of water, more preferably less than typically smaller than 10 weight %, preferably smaller than 5 weight %, 1 weight %.

According to the present invention fluid composition (such as ink composite) in addition may be considered that substantially free of water (0% Water).

In fact, water present in composition is only to be found in the various components of liquid (such as ink) as impurity The water being added.The purity of selected composition is higher, and water content is lower.

When the adhesive and water insoluble other dyestuffs of the fluid composition (such as ink composite) according to the present invention, A small amount of water or not aqueous promotion liquid film, the formation of such as ink film in composition, so as to improve liquid (such as ink) Resistance and adhesion property.

Advantageously, the organic solvent compound of the solvent is selected from：The alcohol of alcohol, particularly low molecule amount, such as fat Fat alcohol, such as ethanol；The ketone of ketone, preferably low molecule amount；The ether of aklylene glycol；The ester and alkylene glycol ether of aklylene glycol Ester, such as acetic acid esters；Dimethylformamide；1-METHYLPYRROLIDONE；Acetal；Ester；Linear or cyclic ether；Cyclic aliphatic hydrocarbon Or straight chain aliphatic hydrocarbons；Aromatic hydrocarbons；And carbonic ester, such as propylene carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate； And their mixture.

The alcohol and ketone of low molecule amount typically refer to alcohol and ketone with 8 carbon atoms or less than 8 carbon atoms.

Preferably, above-mentioned solvated compoundses have dissolving ink other compositions, particularly adhesive, colorant materials, The property of additive etc..

Alcohol is preferably selected from the straight or branched fatty alcohol with 1~8 carbon atoms, such as methanol, ethanol, 1- propyl alcohol, 2- propyl alcohol, n-butanol, 2- butanol, tert-butyl alcohol etc..

Ketone is preferably selected from the ketone with 3~10 carbon atoms, such as acetone, butanone (methyl ethyl ketone), 2 pentanone (first Base propyl group ketone), 3- methyl -2- butanone (methyl isopropyl Ketone) and 4-methyl-2 pentanone (methyl iso-butyl ketone (MIBK)).

The ether of aklylene glycol is preferably selected from including the list of the aklylene glycol of 1~10 carbon atoms in alkylidene chain Alkyl (C1 alkyl~C6 alkyl) ether or dialkyl group (C1 alkyl~C6 alkyl) ether, preferably these alkylene glycol ethers are ethylene glycol Ether or propylene glycol, such as methoxypropanol.

The ester of aklylene glycol and the ester of alkylene glycol ether are preferably selected from the radical of saturated aliphatic with 1~6 carbon atoms The ester of carboxylic acid (such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid).

For example, can be mentioned that Methoxypropylacetate, butyldiglycol acetic acid esters etc..

Ester is preferably selected from the ester of low molecule amount, the formic acid esters of the alcohol such as with 1~10 carbon atoms, acetic acid esters, third Acid esters or butyrate.

Acetal is preferably selected from the acetal of low molecule amount, such as ethylal and dimethoxym ethane.

Ether is preferably selected from low molecule amount ether, such as dioxolanes or tetrahydrofuran.

Those skilled in the art can easily identify that dielectric constant is less than 15 from solvated compoundses exemplified above Compound.

For example can be in table http:In //www.atomer.fr/1/1bcsu.html or in table http:// The organic solvent compound that dielectric constant is less than 15 is found in www.stenutz.eu/chem/solv23.php.

Or, the list of the most common solvent with its dielectric constant can be found in this address：http:// Depts.washington.edu/eooptic/linkfiles/dielectric_chart% 5B1%5D.pdf.

In an identical manner, those skilled in the art can easily identify from solvents listed above compound and wave The solvated compoundses and non-volatile solvated compoundses of hair property.

" volatile organic solvent compound " is typically referred to, the standard based on butyl acetate with the evaporation rate equal to 1, The compound has the evaporation rate more than 0.5.

It is (such as oily according to the fluid composition of the present invention based on the gross weight of the solvent according to preferred embodiment Ink composition) solvent including multi-quantity (50 weight % or more) at least one dielectric constant be less than 15 organic solvent Compound；It is preferred that the solvent includes 90 weight % or more, more preferably 95 weight % or more, more preferably 100 weight % institute Give an account of the organic solvent compound that electric constant is less than 15, that is to say, that the solvent is organic molten less than 15 by the dielectric constant Immunomodulator compounds constitute (composition).

When the solvent of the fluid composition according to the present invention is not as described in being less than 15 according to the dielectric constant of the present invention When organic solvent compound constitutes (composition), the fluid composition can optionally further include one or more dielectric constants Organic solvent compound and/or water more than or equal to 15.

It is (all according to the fluid composition according to the present invention of above-mentioned preferred embodiment based on the gross weight of the solvent Such as ink composite) solvent then may further include small number (being less than 50 weight %) at least one dielectric constant it is big In or equal to 15 organic solvent compound and water；The solvent includes preferably smaller than 10 weight %, more preferably less than 5 weight % The dielectric constant be more than or equal to 15 solvated compoundses.

Preferably, above-mentioned solvent is more than or equal to 15 organic solvent compound and water without (0%) dielectric constant.

Advantageously, organic solvent compound of the dielectric constant less than 15 is selected from volatile organic solvent compound.

Preferably, the solvent is constituted and (constituted) by one or more volatile organic solvent compounds, and the solvent is more It is preferred that the volatile organic solvent compound for being less than 15 by one or more dielectric constants is constituted and (constituted).

It can be mentioned that preferred dielectric constant be less than 15 volatile organic solvent compound have：Dioxolanes, first contracting Aldehyde, diethoxymethane (or ethylal), ester, such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate And dimethyl carbonate.

Had according to the volatility that the solvent of the fluid composition of the present invention can be less than 15 by these preferred dielectric constants One or more in machine solvated compoundses constitute (composition), for example, can be by according to the solvent of fluid composition of the invention Ethyl acetate constitutes (composition), or is constituted and (constituted) by dioxolanes, or by dioxolanes and the mixture of ethylal Constitute (composition), or constituted and (constituted) by the mixture of dioxolanes and dimethyl carbonate.

In the fluid composition according to the present invention, based on the gross weight of the ink composite, the solvent is generally accounted for At least 20 weight %, the solvent preferably accounts for the weight % of 30 weight %~90, more preferably accounts for the weight % of 60 weight %~80.

In order to become to have color or opaque, further wrapped according to the fluid composition (such as ink composite) of the present invention Include colorant materials, such as dyestuff and pigment.

Dyestuff and/or pigment can be selected from all dyestuffs or face well known by persons skilled in the art for being suitable to required purposes Some in material, these pigment or dyestuff have mentioned above.

These dyestuffs and pigment can be used for the continuous injection of " CIJ " deflection in particular selected from well known by persons skilled in the art The dyestuff and pigment of the ink formulations of printing technology.

Above it has been observed that can be with according to the solid particle (such as pigment) that optionally contains of fluid composition of the present invention With specific particle diameter.

The dyestuff can be selected from the known dyestuff of " C.I. solvent dyes " title, and the pigment can be selected from Organic pigment and inorganic pigment, are especially selected from the known dyestuff of " C.I. pigment " title, and selected from " pigment rope Draw " NM solid particle in (C.I.), such as：The particle of metal or alloy, or the mixture of metal particle, such as copper And/or the particle of silver, the particle of metal oxide, ceramic particle, the particle of refractory inorganic compounds, and it is any other inorganic The particle of compound, the pigment is preferably selected from titanium oxide and carbon black.

It can be mentioned that the example of most common pigment and dyestuff has：C.I. solvent black 3,7,27,28,29,35,48,49, C.I. solvent blue 38,44,45,70,79,98,100,129, C.I. solvent red 8s, 49,68,89,124,160,164, C.I. solvents Huang 83:1st, 126,146, green 5, the C.I. solvents orange 97 of 162, C.I. solvents, C.I. solvent browns 20,52, C.I. solvent violets 9；Pigment Indigo plant 15:1、15:3rd, 60 dispersion, the dispersion of pigment Green 7, the dispersion of pigment black 7, pigment red 48:2、144、149、 166th, 185,202,208,214,254 dispersion, the dispersion of pigment violet 19,23, pigment yellow 17,83,93,139,151, 155th, the dispersion of 180,191 dispersion, the dispersion of pigment brown 23,25,41, or Pigment white 6.

It is preferred that dyestuff be C.I. solvent blacks 27 and C.I. solvent blacks 29.

It is preferred that pigment be Pigment white 6, pigment black 7, pigment blue 60, paratonere 202 and pigment Green 7.

Based on the gross weight of the fluid composition, the total amount of dyestuff and/or pigment is usually the weight of 0.05 weight %~25 Measure %, the weight % of preferably 1 weight %~20 weight %, more preferably 3 weight %~10.

Preferably, minimum, the water insoluble dyestuff of the solubility in water will be selected.

Water insoluble dyestuff typically refers to 1 weight % of addition to going in mineral water without causing macroscopic water Coloring dyestuff.

It may further include according to the fluid composition of the present invention and constitute (group by one or more binder polymers Into) adhesive.

These binder polymers can selected from it is known to those skilled in the art be used for prepare CIJ type ink for inking that A little binder polymers.

Above as can be seen that the polymer optionally contained according to the fluid composition of the present invention can have specific molecule Amount.

Advantageously, above-mentioned binder polymer can be selected from (methyl) acrylate copolymer, ethene polymers, ketone polymerization Thing, hydroxyaromatic polymer, cellulosic polymer, styrene polymer, epoxy polymer, polyurethane, polystyrene acrylic acid Ester, polyalkoxysilane, and two or more in them combination.

Advantageously, represented with solid material, based on the gross weight of the fluid composition according to the present invention, described adhesive is accounted for The weight % of 1 weight %~45, preferably accounts for the weight % of 5 weight %~25, more preferably accounts for the weight % of 10 weight %~20.

Advantageously, the weight ratio of adhesive/dyestuff and/or pigment can be more than or equal to 0.5, preferably greater than or equal to 1.

In order that adhesive effectively plays its effect, i.e., make it have actual work(by providing enough mechanical strengths Can, the ratio be 0.5, be preferably 1 minimum value be commonly referred to be it is necessary.

In addition, may include that one or more plasticizer are (viscous according to the fluid composition (such as ink composite) of the present invention The plasticizer of the polymer of mixture), the plasticizer is selected from plasticizer well known by persons skilled in the art and according to institute The adhesive used is selected.

It can be mentioned that as plasticizer, for example thermoplastic polyurethane, phthalic acid ester, adipate ester, citrate With the ester of citric acid, alkyl phosphate, glycerine, lactic acid, oleic acid, polypropylene glycol, fatty acid triglycercide, levulic acid, and Their mixture.

Based on the gross weight of fluid composition (such as ink composite), plasticizer is excellent generally with least 0.05 weight % The weight % of 0.1 weight %~20 amount is selected to exist.

At least one conductive salt can optionally further be included according to the composition of the present invention, it is another except non-ink It is ionizable compound in itself to plant composition (such as dyestuff, pigment or other materials), (can such as be provided when it is dissociated The salt of electric conductivity), and ink is given with enough electric conductivity without adding conductive salt in itself, it is particularly to have been mentioned With " titles of C.I. solvent blacks 27,29,35 and 45 " and known compound.

It is sometimes desirable, however, that including at least one originally according to the fluid composition (such as ink composite) of the present invention The body conductive salt different from ionizable compound (all such as above-mentioned dyestuff, pigment and other compositions).

" conductive salt " typically refers to provide the salt of electric conductivity for fluid composition (such as ink composite).

Therefore the conductive salt can be selected from such as lithium, sodium, the salt of the alkali metal of potassium, the alkaline-earth metal of such as magnesium and calcium Salt, and primary ammonium salt or quaternary ammonium salt；The form of the salt is halide (chloride, bromide, iodide, fluoride), high chlorine Hydrochlorate, nitrate, rhodanate, formates, acetate, sulfate, propionate, trifluoroacetate, trifluoromethyl sulfonic acid (three Fluorine mesylate), hexafluorophosphate, hexafluoro antimonate, tetrafluoroborate, picrate, carboxylate and sulfonate etc..

If must have water resistance with the mark obtained according to the fluid composition (such as ink composite) of the present invention, Then these conductive salts will those conductions selected from water insoluble (solubility i.e., usually in water is less than 0.5 weight %) Property salt, quaternary ammonium and hexafluorophosphate or hexafluoro antimonate such as with aliphatic chain.

Therefore, if it is desirable to if, then at least one conductive salt will be present in fluid composition, to assign combination Thing is with above-mentioned electrical conductivity：Gross weight based on fluid composition, its amount is preferably the weight % of 0.01 weight %~10, more preferably The weight % of 0.01 weight %~1 weight %, more preferably 0.01 weight %~0.05.

Because being usually less than according to the electrical conductivity of the fluid composition of the present invention (such as oily for the liquid of " CIJ " technology Ink), so the amount of the conductive salt optionally added is typically smaller than these liquid for " CIJ ".

One or more additives can be further comprised according to the ink composite of the present invention, the additive, which is selected from, to be improved The solubility of some compositions, printing quality, adhesiveness or further control liquid are for example oily in the composition of above-mentioned ink composite Compound of the ink to the wetability of various carriers.

Above-mentioned additive can be selected from defoamer, chemical stabilizer, UV stabilizer, surfactant, salt (especially Conductive salt) corrosion inhibitor, bactericide, fungicide and biocide, pH value regulation buffer etc..

Whether additive is used with considerably less amount, be defoamer, stabilizer or surfactant according to these additives, Typically less than or equal to 5%, sometimes as little as 0.01%.

Those skilled in the art easily can determine that application is required according to carrier to be marked from these additives Additive.

The invention further relates to as described above according to the fluid composition (such as ink composite) of the present invention using double State deflects the application in the printing machine or print head of continuous jet printing technology, wherein, the fluid composition is in printing process Middle formation is not by the electrically charged drop of electric field, and each drop has zero charge, and each drop forms dipole under electric field action, Then above-mentioned drop is deflected by the electric field.

Therefore the printing technology is so-called " SPI " technology.

The technology, the printing machine, described in print head document as mentioned above [1], [2], [3], [4] or [5] or Their any combination.Printing machine in these these documents individually or as combination especially such as above clearly discussed And print head.

Continuous jet printing technology is deflected by fluid composition (such as ink combination with bifurcation the invention further relates to one kind Thing) it is ejected on substrate, carrier or object (such as porous or non-porous substrate, carrier or object) to print and/or handle And/or the method for marking and/or encoding these substrates, carrier or object, wherein, fluid composition shape in printing process Into by the electrically charged drop of electric field, each drop does not have zero charge, each drop forms dipole under electric field action, then Above-mentioned drop is deflected by the electric field, it is characterised in that the fluid composition (such as ink composite) is root as described above According to the fluid composition (such as ink composite) of the present invention.

Therefore the printing technology is so-called " SPI " technology.

Described in document [1], [2], [3], [4] or [5] as mentioned above, the technology be using the technology process, The technology of method, printing machine and print head individually or as combination.This is especially by the process, side discussed using the technology Printing technology in these documents individually or as combination that method, printing machine and print head are such as above clearly discussed.

The purpose of the present invention or a kind of substrate, carrier or object, for example, porous or non-porous substrate, carrier or thing Body dried by (in substrate or carrier) and/or absorb according to fluid composition (such as pigment ink of the invention there is provided having Composition) and the printing obtained and/or processing and/or mark and/or coding.

The printing and/or the processing and/or the mark and/or the coding generally substantially include all non-wave Hair property solid material, the pigment and/or adhesive of such as fluid composition, and it is by evaporating and/or absorbing in the substrate Other substantially all of volatility or migration component (such as supporting agent, medium of fluid composition (such as ink composite) (vehicle)) obtain.

The substrate can be made of metal, such as made of aluminum, be formed from steel (beverage can)；(glass is made by glass Bottle)；It is made up of ceramics；It is made up of the material of containing cellulose, the material of containing cellulose is such as glassine paper, paper, optionally have painting Layer or glossiness paper, cardboard or timber；It is made up, is particularly made up of thermoplastic polymer (" plastics ") of organic polymer, The form of thermoplastic polymer especially film, is selected from PVDC, PVC, polyester, such as PET, polyethylene (PE), polypropylene (PP) Polyolefin；It is made up of poly- (methyl methacrylate) PMMA (also referred to as " Plexiglas ")；It is made up of fabric；By weaving Product are made；It is made up of natural rubber or synthetic rubber；Or be made up of any other non-porous or porous material；Or by a variety of The composite of above-mentioned material is made.

Substrate can by cotton into, be made up of spun rayon (" Fibranne "), by viscose rayon, polyester, wool or they Mixture be made.

In all substrates and particularly in flexible substrate or even very obtain superior quality in flexible substrate Printing and/or processing and/or mark and/or coding.

Embodiment

Read property as an example and after following embodiments of the invention that non-limiting example is provided, it will more preferably Ground understands the present invention.

Embodiment 1~4：

In all these embodiments, the ink composite according to the present invention is prepared for.

These ink composites are included in the component shown in table 1 with the ratio shown in table 1.

These compositions are generally prepared by simply mixing each component.

In tablei, according to each ink composite, the dielectric constant of each composition solvent, the electrical conductivity of composition be also show (μ S/cm) and viscosity (mPa.s=cPs), and finally determine ink whether be suitable to deflection continuous injection technology (CIJ) or So-called " SPI " technology is printed.

Table I-ink composite

With byConductivity meter measurement electrical conductivity commercially available from company.

Dynamic viscosity is measured using " Couette " the type coaxial cylinder viscometer from Contraves companies.

The property of ink component is as follows：

In the prototype printing machine using nozzle diameter for 40 μm of so-called " SPI " technology, 1~embodiment of embodiment 4 Composition provides suitable printing on the plastic film.

In addition, demonstrating：1~embodiment of embodiment 4 can not possibly be used in the printing machine for implementing so-called " CIJ " technology Composition, unlikely obtain suitable printing.

Claims

1. being the fluid composition of liquid at room temperature, such as ink composite, the fluid composition is used in particular for inclined with bifurcation Turn continuous jet printing technology print fluid composition, wherein, the fluid composition formed in printing process not by The electrically charged drop of electric field, each drop has zero charge, and each drop forms dipole under electric field action, then the drop Deflected by the electric field, it is characterised in that the fluid composition includes：

A) solvent containing one or more organic solvent compounds and optional water, the solvent totally has Jie less than 15 Electric constant；

B) adhesive；

C) one or more dyestuffs and/or pigment；

And：

D) electrical conductivity of the fluid composition at 20 DEG C is less than or equal to 200 μ S/cm, preferably lower than or equal to 150 μ S/ Cm, more preferably less than or equal to 100 μ S/cm.

2. fluid composition according to claim 1, such as ink composite, electricity of the fluid composition at 20 DEG C Conductance is more than or equal to 1 μ S/cm, 2 μ S/cm, 3 μ S/cm, 4 μ S/cm, 5 μ S/cm, 6 μ S/cm, 7 μ S/cm, 8 μ S/cm, 9 μ S/cm Or 10 μ S/cm.

3. fluid composition according to any one of the preceding claims, such as ink composite, the ink composite Electrical conductivity at 20 DEG C is the μ S/cm of 1 μ S/cm~200, the μ of particularly 2 μ S/cm~150 μ S/cm, particularly 5 μ S/cm~100 The μ S/cm of S/cm, or even 10 μ S/cm~100.

4. fluid composition according to any one of the preceding claims, wherein, the organic solvent chemical combination in the solvent Thing is selected from：The alcohol of alcohol, particularly low molecule amount, such as fatty alcohol, such as ethanol；The ketone of ketone, preferably low molecule amount；Alkylidene two The ether of alcohol；The ester of aklylene glycol and the ester of alkylene glycol ether, such as acetic acid esters；Dimethylformamide；N- crassitudes Ketone；Acetal；Ester；Linear or cyclic ether；Cyclic aliphatic hydrocarbon or straight chain aliphatic hydrocarbons；Aromatic hydrocarbons；And carbonic ester, such as polypropylene carbonate Ester, ethylene carbonate and dimethyl carbonate and diethyl carbonate；And their mixture.

5. fluid composition according to any one of the preceding claims, wherein, it is described based on the gross weight of the solvent At least one dielectric constant that solvent includes multi-quantity (gross weight relative to the solvent is 50 weight % or more) is less than 15 organic solvent compound；It is preferred that the solvent includes 90 weight % or more, more preferably 95 weight % or more, more preferably The 100 weight % dielectric constant is less than 15 organic solvent compound.

6. fluid composition according to claim 5, wherein, based on the gross weight of the solvent, the solvent is further At least one dielectric constant including small number (gross weight relative to the solvent is less than 50 weight %) is more than or equal to 15 organic solvent compound and water；It is preferred that the solvent includes being less than 10 weight %, more preferably less than 5 weight %'s is given an account of Electric constant is more than or equal to 15 organic solvent compound and water.

7. fluid composition according to any one of the preceding claims, wherein, the dielectric constant is organic less than 15 Solvated compoundses are selected from volatile organic solvent compound.

8. fluid composition according to any one of the preceding claims, wherein, the solvent is volatilized by one or more Property organic solvent compound group be preferably less than into, the solvent by one or more dielectric constants 15 volatile organic solvent Compound is constituted.

9. the composition according to any one of claim 7 and 8, wherein, the volatility that the dielectric constant is less than 15 has Machine solvated compoundses be selected from dioxolanes, dimethoxym ethane, diethoxymethane (or ethylal), ester, such as ethyl acetate, Propyl acetate, isopropyl acetate, butyl acetate and dimethyl carbonate.

10. the fluid composition according to any one of claim, wherein, based on the gross weight of the fluid composition, The solvent accounts at least 20 weight %, and the solvent preferably accounts for the weight % of 30 weight %~90, more preferably accounts for 60 weight %~80 Weight %.

11. fluid composition according to any one of the preceding claims, wherein, the dyestuff is selected from " C.I. solvents The known dyestuff of dyestuff " title, and the pigment is selected from organic pigment and inorganic pigment, is especially selected from " C.I. face Material " the known pigment of title, and NM solid particle in " pigment index " (C.I.) is selected from, such as：Metal or The particle of the particle of metal alloy or metal mixture, such as copper and/or silver, the particle of metal oxide, ceramic particle is resistance to The particle of fiery inorganic compound, and any other inorganic compound particle, preferably described pigment be selected from titanium oxide and carbon black.

12. fluid composition according to claim 11, wherein, " solvent dye " be selected from C.I. solvent black 3s, 7, 27th, 28,29,35,48,49, C.I. solvent blues 38,44,45,70,79,98,100,129, C.I. solvent red 8s, 49,68,89, 124th, 160,164, C.I. solvent yellows 83:1st, 126,146, green 5, the C.I. solvents orange 97 of 162, C.I. solvents, C.I. solvent browns 20, 52 and C.I. solvent violets 9；And " the C.I. pigment " is selected from pigment blue 15:1、15:3rd, 60 dispersion, pigment Green 7 it is scattered Body, the dispersion of pigment black 7, pigment red 48:2nd, 144,149,166,185,202,208,214,254 dispersion, pigment violet 19th, 23 dispersion, pigment yellow 17,83,93,139,151,155,180,191 dispersion, pigment brown 23,25,41 it is scattered Body, or Pigment white 6 dispersion.

13. fluid composition according to any one of the preceding claims, based on the gross weight of the fluid composition, institute Stating fluid composition includes the weight % of 0.05 weight %~25 dyestuff and/or pigment, the weight % of preferably 1 weight %~20 dye Material and/or pigment, the weight % of more preferably 3 weight %~10 dyestuff and/or pigment.

14. fluid composition according to any one of the preceding claims, wherein, described adhesive is viscous by one or more Binder polymer is constituted, and preferably described adhesive polymer is selected from (methyl) acrylate copolymer, ethene polymers, ketone polymerization Thing, hydroxyaromatic polymer, cellulosic polymer, styrene polymer, epoxy polymer, polyurethane, cinnamic acrylic ester Copolymer, polyalkoxysilane, and they two or more combination.

15. fluid composition according to claim 14, wherein, it is described viscous based on the gross weight of the fluid composition Mixture accounts for the weight % of 1 weight %~45, preferably accounts for the weight % of 5 weight %~25, more preferably accounts for the weight % of 10 weight %~20.

16. fluid composition according to any one of the preceding claims, wherein, described adhesive and the dyestuff and/ Or the weight ratio of the pigment is more than or equal to 0.5, preferably greater than or equal to 1.

17. fluid composition according to any one of the preceding claims, based on the gross weight of the fluid composition, institute State one kind or many that fluid composition further comprises that content is the weight % of at least 0.05 weight %, preferably 0.1 weight %~20 Plant plasticizer.

18. fluid composition according to any one of the preceding claims, based on the gross weight of the fluid composition, institute State fluid composition and further comprise that content is the weight % of 0.01 weight %~10, the weight % of preferably 0.01 weight %~1, more preferably For the weight % of 0.01 weight %~0.05 at least one conductive salt.

19. fluid composition according to claim 18, wherein, the conductive salt is selected from the alkali gold of such as lithium, sodium, potassium The salt of the alkaline-earth metal of the salt of category, such as magnesium and calcium, and primary ammonium salt or quaternary ammonium salt；The form of the salt is halide, high chlorine Hydrochlorate, nitrate, rhodanate, formates, acetate, sulfate, propionate, trifluoroacetate, trifluoromethyl sulfonic acid (three Fluorine mesylate), hexafluorophosphate, hexafluoro antimonate, tetrafluoroborate, picrate, carboxylate and sulfonate.

20. fluid composition according to any one of the preceding claims, the fluid composition further comprises one kind Or multiple additives, the additive is selected from defoamer, chemical stabilizer, UV stabilizer, surfactant, salt corrosion suppression Agent, bactericide, fungicide and biocide, and pH regulation buffers.

21. fluid composition according to any one of the preceding claims, it is characterised in that when the fluid composition bag When including at least one polymer being dissolved in the solvent of the fluid composition, the weight average molecular weight of the polymer is more than The dalton of 70000 dalton, preferably 75000 dalton~200000, the dalton of more preferably 80000 dalton~200000.

22. fluid composition according to any one of the preceding claims, it is characterised in that when the fluid composition bag When including solid particle, the full-size of the solid particle is 2 μm~10 μm, preferably 2 μm~5 μm.

23. the fluid composition according to any one of claim 1~22, such as ink composite, inclined using bifurcation Turn the application in the printing machine or print head of continuous jet printing technology, wherein, fluid composition shape in printing process Into by the electrically charged drop of electric field, each drop does not have zero charge, and dipole is formed under electric field action, then the drop Deflected by the electric field.

24. deflecting continuous jet printing technology by fluid composition with bifurcation, such as ink composite is ejected into substrate, carrier Or object, such as print on porous or non-porous substrate, carrier or object and/or handle and/or mark and/or encode this The method of a little substrates, carrier or object, wherein, the fluid composition forms not electrically charged by electric field in printing process Drop, each drop has zero charge, and dipole is formed under electric field action, and then the drop is deflected by the electric field, and it is special Levy and be, the fluid composition, such as ink composite are the liquid groups according to any one of claim 1~22 Compound, such as ink composite.

25. substrate, carrier or object, such as porous or non-porous substrate, carrier or object there is provided having by drying and/or Absorb fluid composition according to any one of claim 1~22 and the printing and/or processing that obtain and/or mark And/or coding.

26. substrate according to claim 25, carrier or object, it is characterised in that the substrate is made up of following material： Metal, such as aluminium；Steel；Glass；Ceramics；The material of containing cellulose, such as glassine paper, paper, optionally there is coating or glossiness Paper, cardboard or timber；Organic polymer, particularly thermoplastic polymer (" plastics "), be selected from PVDC, PVC, polyester, The polyolefin of PET, such as polyethylene (PE), polypropylene (PP)；Poly- (methyl methacrylate) PMMA (" Plexiglas ")；Knit Thing；Textile；Natural rubber or synthetic rubber；Or any other non-porous or porous material；Or a variety of above-mentioned materials Composite.